A series of narrow band-gap conjugated copolymers (PFO-DDQ) derived from 9,9-dioctylfluorene (DOF) and 2,3-dimethyl-5,8-dithien-2-yl-quinoxalines (DDQ) is prepared by the palladium-catalyzed Suzuki coupling reaction with the molar feed ratio of DDQ at around 1%, 5%, 15%, 30% and 50%, respectively. The obtained polymers are readily soluble in common organic solvents. The solutions and the thin solid films of the copolymers absorb light from 300–590 nm with two absorbance peaks at around 380 and 490 nm. The intensity of 490 nm peak increases with the increasing DDQ content in the polymers. Efficient energy transfer due to exciton trapping on narrow-band-gap DDQ sites has been observed. The PL emission consists exclusively of DDQ unit emission at around 591–643 nm depending on the DDQ content in solid film. The EL emission peaks are red-shifted from 580 nm for PFO-DDQ1 to 635 nm for PFO-DDQ50. The highest external quantum efficiency achieved with the device configuration ITO/PEDOT/PVK/PFO-DDQ15/Ba/Al is 1.33% with a luminous efficiency 1.54 cd/A. Bulk heterojunction photovoltaic cells fabricated from composite films of PFO-DDQ30 copolymer and [6,6]-phenyl C butyric acid methyl ester (PCBM) as electron donor and electron acceptor, respectively in device configuration: ITO/PEDOT:PSS/PFO-DDQ30:PCBM/PFPNBr/Al shows power conversion efficiencies of 1.18% with open-circuit voltage () of 0.90 V and short-circuit current density () of 2.66 mA/cm under an AM1.5 solar simulator (100 mW/cm). The photocurrent response wavelengths of the PVCs based on PFO-DDQ30/PCBM blends covers 300–700 nm. This indicates that these kinds of low band-gap polymers are promising candidates for polymeric solar cells and red light-emitting diodes.